Homogenous, stabilized, reduced metal addition polymerization catalysts, process for preparation and method of use

ABSTRACT

Complexes useful as addition polymerization catalysts, a process for their manufacture and addition polymerization processes wherein the complex comprises a Group 4 metal in the  +  3 oxidation state, a delocalized n-bonding moiety, and at least one stabilizing ligand.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 08/008,003 filed Jan. 21,1993, now U.S. Pat. No. 5,374,696 which is a continuation-in-part ofapplication Ser. No. 07/941,014, filed Sep. 4, 1992, now abandoned whichis a continuation-in-part of application Ser. No. 857,886, filed Mar.26, 1992, now abandoned, the teachings of which are hereby incorporatedby reference.

BACKGROUND OF THE INVENTION

This invention relates to the use of catalysts comprising certainstabilized, reduced metal complexes in the polymerization of olefinpolymers. In one embodiment such catalysts additionally employ anactivating cocatalyst. In another embodiment such catalysts may beemployed with or without an activating cocatalyst. Finally the inventionrelates to an improved method for preparing the stabilized reduced metalcomplexes. The compositions are especially useful as catalysts for thepolymerization of olefins such as ethylene for polymers having utilityas molding resins and in the formation of foamed products havingcushioning and insulating applications and films that are useful asprotective wrappings.

In U.S. Ser. No. 545,403, filed Jul. 3, 1990 (equivalent toEP-A-416,845) there are disclosed and claimed certainmonocyclopentadienyl metal complexes having utility as homogeneousolefin polymerization catalysts. In U.S. Pat. No. 5,064,802 (equivalentto EP-A-418,044), cationic monocyclopentadienyl metal complexes withsalts of Bronsted acids containing a non-coordinating compatible anionare disclosed and claimed. Finally, in U.S. Ser. No. 547,718, also filedon Jul. 3, 1990 (EP-A-468,651), an oxidative activation technique forpreparing such cationic catalysts is disclosed and claimed. For theteachings contained therein the above mentioned pending U.S.applications and U.S. patent are herein incorporated in their entiretyby reference thereto.

In J. Am. Chem. Soc. 113, 3623-3625 (1991) there is disclosed a processfor preparation of "cation like" zirconocene polymerization complexes byalkyl abstraction using tris(pentafluorophenyl)borane. The complexeswere stated to have activity roughly comparable to typical complexesemploying alumoxane. No suggestion as to the suitability of thedisclosed technique for use with reduced oxidation state metal catalystsis provided by the reference.

In U.S. Pat. No. 4,057,565 there are disclosed Ti, Zr, or Hf derivativesof 2-dialkylaminobenzyl or 2-dialkylaminomethylphenyl all in the +4oxidation state which are useful as components of catalysts for olefinpolymerization. No mention is given for +3 oxidation state metalcatalysts.

In J. Am. Chem. Soc. 100, 8068-8073 (1978) there is mentioned thesynthesis and characterization of Ti(+3) complexes containingcyclopentadienyl groups and 2-dialkylaminobenzyl or2-dialkylaminomethylphenyl groups. No mention of utility as additionpolymerization catalysts is given.

In U.S. Pat. No. 4,870,042, catalysts for olefin polymerizationscomprising a pyrazolyl borate complex of titanium or zirconium compoundsincluding titanium trichloride (Example 4) are disclosed.

In Organometallics, 10, 3227-3237 (1991) certain titanium +3 complexescontaining cyclopentadienyl groups and alkyl groups are mentioned. Onpage 3236, the reference states:

"So far no well-defined neutral titanium-based molecular system withestablished activity for catalytic olefin polymerization has beendescribed. . . Apparently, the tervalent Cp*₂ TiR system cannot inducesufficient positive charge at the β-carbon atom of an incoming ethylenemolecule to reach the polar transition state for migratory insertion."

In Journal of Organometallic Chemistry, 334 (1987) C1-C4, η³-allyl(bis-η⁵ -cyclopentadienyl)titanium (III) activated withdimethylaluminum chloride was found to create a coordinated species Cp₂Ti (allyl)--(CH₃)₂ AlCl which was found to polymerize ethylene. Use ofstronger Lewis acids so as to cause ligand abstraction therebydestroying the requisite carbon-titanium bond was to be avoidedaccording to the reference.

In accordance with the present invention there is provided an additionpolymerization catalyst comprising in combination:

a metal complex, A₁, corresponding to the formula:

    Cp.sub.2 ML,                                               (Ia)

wherein:

Cp independently each occurrence is a cyclopentadienyl group n-bound toM, or a hydrocarbyl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloidor halohydrocarbylmetalloid substituted derivative of saidcyclopentadienyl group, said Cp containing up to 50 nonhydrogen atoms,and optionally both Cp groups may be joined together by a bridginggroup;

M is a metal of Group 4 of the Periodic Table of the Elements in the ⁺ 3oxidation state;

L is a monovalent anionic stabilizing ligand selected from the groupconsisting of: alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy,aryloxy, sulfido groups and mixtures thereof, and being furthersubstituted with an amine, phosphine, ether, or thioether containingsubstituent able to form a coordinate-covalent bond or chelating bondwith M; said ligand having up to 50 nonhydrogen atoms;

and an activating cocatalyst.

Preferably in accordance with the present invention the ratio of metalcomplex to activating cocatalyst is from 1:0.01 to 1:10⁶.

In a further embodiment there is provided an addition polymerizationcatalyst comprising in combination:

a metal complex, A₂, corresponding to the formula

    Cp'ML'.sub.2,                                              (Ib)

wherein:

Cp' is a cyclopentadienyl group, or a hydrocarbyl, silyl, halo,halohydrocarbyl, or hydrocarbylmetalloid substituted derivative thereof,said Cp' containing up to 50 nonhydrogen atoms;

M is a metal of Group 4 of the Periodic Table of the Elements in the ⁺ 3oxidation state;

L' independently each occurrence is hydride, halo, or a monovalentanionic ligand selected from the group consisting of hydrocarbyl, silyl,amido, phosphido, alkoxy, aryloxy, and sulfido groups; mixtures thereof;and amine, phosphine, ether, and thioether derivatives of the foregoing,said ligand having up to 50 nonhydrogen atoms, with the proviso that inat least one occurrence L' is a stabilizing ligand comprising an amine,phosphine, ether or thioether functionality able to form acoordinate-covalent bond or chelating bond with M, or comprising anethylenic unsaturation able to form an η3 bond with M;

and an activating cocatalyst.

Preferably the activating cocatalyst is present in an amount to providea ratio of metal complex to activating cocatalyst from 1:0.01 to 1:10⁶.

In a still further embodiment of the present invention there is provideda metal complex, A₃, corresponding to the formula: ##STR1## wherein:

M is a metal of Group 4 of the Periodic Table of the Elements in the ⁺ 3oxidation state;

Cp" is a cyclopentadienyl group, or a hydrocarbyl, silyl, halo,halohydrocarbyl, or hydrocarbylmetalloid substituted derivative thereof,said Cp" containing up to 50 nonhydrogen atoms;

Z is a divalent moiety comprising oxygen, nitrogen, phosphorous, boron,or a member of Group 14 of the Periodic Table of the Elements saidmoiety having up to 30 nonhydrogen atoms;

Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfurcovalently bonded to M and Z through said nitrogen, phosphorus, oxygenor sulfur atom, the ligand moiety consisting of --Cp"--Z--Y-- beingdianionic and having the ionic charges residing formally on Cp" and Y;and

L" is a stabilizing ligand selected from the group consisting of L andC₃₋₁₀ hydrocarbyl groups comprising an ethylenic unsaturation able toform an η3 bond with M.

The above complexes, A₃, are suitable for use in polymerization ofaddition polymerizable monomers alone or optionally in the presence ofan activating cocatalyst. When present, the activating cocatalyst ispreferably used in an amount to provide a ratio of metal complex toactivating cocatalyst from 1:0.01 to 1:10⁶.

DETAILED DESCRIPTION

The metal complexes, A₁, may be prepared by a process comprisingcontacting a Group 4 metal complex corresponding to the formula:

    Cp.sub.2 M*XL                                              (IIa)

wherein Cp and L are as previously defined, and

M* is a metal of Group 4 of the Periodic Table of the Elements in the ⁺4 oxidation state; and

X is halide or C₁₋₁₀ hydrocarbyloxide,

with a reducing agent under reducing conditions to form the Group 4metal complex.

The metal complexes, A₂, may be prepared by a process comprisingcontacting a Group 4 metal complex corresponding to the formula:

    Cp'M*XL'.sub.2                                             (IIb)

wherein Cp' and L' are as previously defined, and

M* is a metal of Group 4 of the Periodic Table of the Elements in the ⁺4 oxidation state; and

X is halide or C₁₋₁₀ hydrocarbyloxide,

with a reducing agent under reducing conditions to form the Group 4metal complex.

Finally, the metal complexes, A₃, may be prepared by a processcomprising contacting a Group 4 metal complex corresponding to theformula: ##STR2## wherein Cp", Z, Y, M*, X and L" are as previouslydefined, with a reducing agent under reducing conditions to form theGroup 4 metal complex.

There are also provided olefin polymerization processes comprising apolymerizable olefin or mixture thereof with the foregoing catalystsunder polymerization conditions and recovering the resulting polymer.

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1989. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups.

By the term "stabilizing ligand" is meant that the ligand groupstabilizes the metal complex through either:

1) a nitrogen, phosphorus, oxygen or sulfur chelating bond, or

2) an η³ bond with a resonant, delocalized n-electronic structure.

Examples of stabilizing ligands of group 1) for use according to thepresent invention include silyl, hydrocarbyl, amido or phosphido ligandssubstituted with one or more aliphatic or aromatic ether-, thioether,amine or phosphine functional groups, especially such amine or phosphinegroups that are tertiary substituted, said stabilizing ligand havingfrom 3 to 30 nonhydrogen atoms. Most preferred group 1) stabilizingligands are 2-dialkylaminobenzyl or 2-(dialkylaminomethyl)phenyl groupscontaining from 1 to 4 carbons in the alkyl groups.

Examples of stabilizing ligands of group 2) for use according to thepresent invention, include C₃₋₁₅ hydrocarbyl groups containing ethylenicunsaturation, such as allyl, 1-methylallyl, 2-methylallyl,1,1-dimethylallyl, or 1,2,3-trimethylallyl groups.

Preferred substituents of the groups Cp, Cp' and Cp" are hydrocarbyl,hydrocarbylene, halosubstituted hydrocarbyl groups having from 1 to 30carbons, and C₁₋₃₀ hydrocarbyl or halohydrocarbyl substituted metalloidradicals wherein the metalloid is an element from Group 14 of thePeriodic Table of the Elements.

Exemplary hydrocarbyl radicals include straight and branched alkylradicals, cyclic aliphatic hydrocarbon radicals, alkyl-substitutedcyclic aliphatic hydrocarbon radicals, aromatic radicals andalkyl-substituted aromatic radicals. Preferred are methyl, ethyl, butyland phenyl radicals. Exemplary organo-metalloid radicals includestraight and branched chain silyl radicals, alkyl-substituted silylradicals, germyl radicals and divalent derivatives of the foregoing.Preferred are trimethylsilyl, triethylsilyl, ethyldimethylsilyl,methyldiethylsilyl, dimethyl-t-butylsilyl, triphenylsilyl,triphenylgermyl, and trimethylgermyl radicals.

More particularly, suitable cyclopentadienyl or substitutedcyclopentadienyl groups in complexes A₁ are illustrated by the formula:##STR3## wherein:

R' is hydrogen, or a group selected from silyl, hydrocarbyl, andcombinations thereof having up to 30 carbon or silicon atoms, or two R'groups together form a divalent derivative of such group.

Preferably, R' independently each occurrence is hydrogen, methyl, ethyl,propyl, butyl, pentyl, hexyl, (including where appropriate all isomers),cyclopentyl, cyclohexyl, norbornyl, benzyl, or phenyl or two R' groupsare linked together thereby forming an indenyl, tetrahydroindenyl,fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group in place ofthe cyclopentadienyl group.

Exemplary metal complexes of formula A₁ are:bis(methylcyclopentadienyl)titanium 2-dimethylaminobenzyl,bis(methylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl,bis(ethylcyclopentadienyl)titanium 2-dimethylaminobenzyl,bis(ethylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl,bis(n-butylcyclopentadienyl)titanium 2-dimethylaminobenzyl,bis(t-butylcyclopentadienyl)titanium 2-dimethylaminobenzyl,bis(n-butylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl,bis(t-butylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl,bis(pentamethylcyclopentadienyl)titanium 2-dimethylaminobenzyl,bis(pentamethylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl,bis(indenyl) 2-dimethylaminobenzyl, bis(indenyl)titanium2-dimethylaminomethylphenyl, bis(fluorenyl) 2-dimethylaminobenzyl,bis(fluorenyl)titanium 2-dimethylaminomethylphenyl,bis(cyclopentadienyl)zirconium 2-dimethylaminobenzyl,bis(cyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,bis(methylcyclopentadienyl)zirconium 2-dimethylaminobenzyl,bis(methylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,bis(ethylcyclopentadienyl)zirconium 2-dimethylaminobenzyl,bis(ethylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,bis(n-butyl cyclopentadienyl)zirconium 2-dimethylaminobenzyl,bis(t-butylcyclopentadienyl)zirconium 2-dimethylaminobenzyl,bis(n-butylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,bis(t-butylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,bis(pentamethylcylopentadienyl)zirconium 2-dimethylaminobenzyl,bis(pentamethylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,bis(indenyl) 2-dimethylaminobenzyl, bis(indenyl)zirconium2-dimethylaminomethylphenyl, bis(fluorenyl) 2-dimethylaminobenzyl,bis(fluorenyl)zirconium 2-dimethylaminomethylphenyl,bis(cyclopentadienyl)hafnium 2-dimethylaminobenzyl,bis(cyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,bis(methylcyclopentadienyl)hafnium 2-dimethylaminobenzyl,bis(methylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,bis(ethylcyclopentadienyl)hafnium 2-dimethylaminobenzylbis(ethylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,bis(butylcyclopentadienyl)hafnium 2-dimethylaminobenzyl,bis(butylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,bis(pentamethylcyclopentadienyl)hafnium 2-dimethylaminobenzyl,bis(pentamethylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,bis(indenyl) 2-dimethylaminobenzyl, bis(indenyl)hafnium2-dimethylaminomethylphenyl, bis(fluorenyl)hafnium2-dimethylaminobenzyl, and bis(fluorenyl)hafnium2-dimethylaminomethylphenyl.

Additional bis-cyclopentadienyl compounds of formula A₁ include thosecontaining a bridging group linking the cyclopentadienyl groups.Preferred bridging groups are those corresponding to the formula(ER"₂)_(x) wherein E is silicon or carbon, R", independently eachoccurrence is hydrogen or a group selected from silyl, hydrocarbyl andcombinations thereof, said R" having up to 30 carbon or silicon atoms,and x is 1 to 8. Preferably R" independently each occurrence is methyl,benzyl, tert-butyl, or phenyl.

Examples of the foregoing bridged cyclopentadienyl group containingcomplexes are compounds corresponding to the formula: ##STR4## wherein:

M, L, E, R' R" and x are as previously defined.

Such bridged structures are especially suited for the preparation ofpolymers having stereoregular molecular structure. In such capacity itis preferred that the complex be nonsymmetrical or possess a chiral,stereorigid structure. Examples of the first type are compoundspossessing different delocalized n-bonded systems, such as onecyclopentadienyl group and one indenyl group. Similar systems based onTi(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefinpolymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980).Examples of chiral structures include bis-indenyl complexes. Similarsystems based on Ti(IV) or Zr(IV) were disclosed for preparation ofisotactic olefin polymers in Wild et al., J. Organomet. Chem, 232,233-47, (1982).

Exemplary bridged cyclopentadienyl complexes of formula Ia are:(dimethylsilyl-bis-cyclopentadienyl) titanium 2-dimethylaminobenzyl,(dimethylsilyl-bis-cyclopentadienyl) titanium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-methylcyclopentadienyl)titanium 2-dimethylaminobenzyl,(dimethylsilyl-bis-methylcyclopentadienyl) titanium2-dimethylaminomethylphenyl,(dimethylsilyl-bis-ethylcyclopentadienyl)titanium 2-dimethylaminobenzyl,(dimethylsilyl-bis-ethylcyclopentadienyl) titanium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-n-butylcyclopentadienyl)titanium 2-dimethylaminobenzyl,(dimethylsilyl-bis-t-butylcyclopentadienyl) titanium2-dimethylaminobenzyl, (dimethylsilyl-bis-n-butylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl,(dimethylsilyl-bis-t-butylcyclopentadienyl) titanium2-dimethylaminomethylphenyl,(dimethylsilyl-bis-tetramethylcyclopentadienyl) titanium2-dimethylaminobenzyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl)titanium 2-dimethylaminomethylphenyl, (dimethylsilyl-bis-indenyl)titanium 2-dimethylaminobenzyl, (dimethylsilyl-bis-indenyl) titanium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-tetrahydroindenyl)titanium 2-dimethylaminobenzyl, (dimethylsilyl-bis-tetrahydroindenyl)titanium 2-dimethylaminomethylphenyl, (dimethylsilyl-bis-fluorenyl)titanium 2-dimethylaminobenzyl, (dimethylsilyl-bis-fluorenyl) titanium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-tetrahydrofluorenyl)titanium 2-dimethylaminobenzyl, (dimethylsilyl-bis-tetrahydrofluorenyl)titanium 2-dimethylaminomethylphenyl,(dimethylsilylcyclopentadienyl-fluorenyl) titanium2-dimethylaminobenzyl, (dimethylsilyl-cyclopentadienyl-fluorenyl)titanium 2-dimethylaminomethylphenyl,(isopropylidene-cyclopentadienyl-fluorenyl) titanium2-dimethylaminobenzyl, (isopropylidene-cyclopentadienyl-fluorenyl)titanium 2-dimethylaminomethylphenyl,(dimethylsilyl-bis-cyclopentadienyl) zirconium 2-dimethylaminobenzyl,(dimethylsilyl-bis-cyclopentadienyl) zirconium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-methylcyclopentadienyl)zirconium 2-dimethylaminobenzyl,(dimethylsilyl-bis-methylcyclopentadienyl) zirconium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-ethylcyclopentadienyl)zirconium 2-dimethylaminobenzyl,(dimethylsilyl-bis-ethylcyclopentadienyl) zirconium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-t-butylcyclopentadienyl)zirconium 2-dimethylaminobenzyl,(dimethylsilyl-bis-n-butylcyclopentadienyl) zirconium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-t-butylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl,(dimethylsilyl-bis-tetramethylcyclopentadienyl) zirconium2-dimethylaminobenzyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl)zirconium 2-dimethylaminomethylphenyl, (dimethylsilyl-bis-indenyl)zirconium 2-dimethylaminobenzyl, (dimethylsilyl-bis-indenyl) zirconium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-tetrahydroindenyl)zirconium 2-dimethylaminobenzyl, (dimethylsilyl-bis-tetrahydroindenyl)zirconium 2-dimethylaminomethylphenyl, (dimethylsilyl-bis-fluorenyl)zirconium 2-dimethylaminobenzyl, (dimethylsilyl-bis-fluorenyl) zirconium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-tetrahydrofluorenyl)zirconium 2-dimethylaminobenzyl, (dimethylsilyl-bis-tetrahydrofluorenyl)zirconium 2-dimethylaminomethylphenyl,(dimethylsilyl-cyclopentadienyl-fluorenyl) zirconium2-dimethylaminobenzyl, (dimethylsilyl-cyclopentadienyl-fluorenyl)zirconium 2-dimethylaminomethylphenyl(isopropylidene-cyclopentadienyl-fluorenyl) zirconium2-dimethylaminobenzyl, (isopropylidene-cyclopentadienyl-fluorenyl)zirconium 2-dimethylaminomethylphenyl,(dimethylsilyl-bis-cyclopentadienyl) hafnium 2-dimethylaminobenzyl,(dimethylsilyl-bis-cyclopentadienyl) hafnium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-methylcyclopentadienyl)hafnium 2-dimethylaminobenzyl,(dimethylsilyl-bis-methylcyclopentadienyl) hafnium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-ethylcyclopentadienyl)hafnium 2-dimethylaminobenzyl, (dimethylsilyl-bis-ethylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,(dimethylsilyl-bis-t-butylcyclopentadienyl) hafnium2-dimethylaminobenzyl, (dimethylsilyl-bis-n-butylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl,(dimethylsilyl-bis-t-butylcyclopentadienyl) hafnium2-dimethylaminomethylphenyl,(dimethylsilyl-bis-tetramethylcyclopentadienyl) hafnium2-dimethylaminobenzyl, (dimethylsilyl-bis-tetramethylcyclopentadienyl)hafnium 2-dimethylaminomethylphenyl, (dimethylsilyl-bis-indenyl) hafnium2-dimethylaminobenzyl, (dimethylsilyl-bis-indenyl) hafnium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-tetrahydroindenyl)hafnium 2-dimethylaminobenzyl, (dimethylsilyl-bis-tetrahydroindenyl)hafnium 2-dimethylaminomethylphenyl, (dimethylsilyl-bis-fluorenyl)hafnium 2-dimethylaminobenzyl, (dimethylsilyl-bis-fluorenyl) hafnium2-dimethylaminomethylphenyl, (dimethylsilyl-bis-tetrahydrofluorenyl)hafnium 2 -dimethylaminobenzyl, (dimethylsilyl-bis-tetrahydrofluorenyl)hafnium 2-dimethylaminomethylphenyl,(dimethylsilyl-cyclopentadienyl-fluorenyl) hafnium2-dimethylaminobenzyl, (dimethylsilyl-cyclopentadienyl-fluorenyl)hafnium 2-dimethylaminomethylphenyl,(isopropylidene-cyclopentadienyl-fluorenyl) hafnium2-dimethyaminobenzyl, and (isopropylidene-cyclopentadienyl-fluorenyl)hafnium 2-dimethylaminomethylphenyl,[2,2'-biphenyldiylbis(3,4-dimethyl-1-cyclopentadienyl)]titanium2-dimethylaminobenzyl,[6,6'-dimethyl-2,2'biphenylbis(3,4-dimethyl-1-cyclopentadienyl)]titanium2-dimethylamino benzyl.

Exemplary complexes of formula A₂ include cyclopentadienyl titaniumallyl chloride, methylcyclopentadienyl titanium allyl chloride,ethylcyclopentadienyl titanium allyl chloride, t-butylcyclopentadienyltitanium allyl chloride, n-butylcyclopentadienyl titanium allylchloride, pentamethylcyclopentadienyl titanium allyl chloride,cyclopentadienyl titanium allyl bromide, methylcyclopentadienyl titaniumallyl bromide, ethylcyclopentadienyl titanium allyl bromide,t-butylcyclopentadienyl titanium allyl bromide, n-butylcyclopentadienyltitanium allyl bromide, pentamethylcyclopentadienyl titanium allylbromide, cyclopentadienyl titanium allyl methoxide,methylcyclopentadienyl titanium allyl methoxide, ethylcyclopentadienyltitanium allyl methoxide, t-butylcyclopentadienyl titanium allylmethoxide, n-butylcyclopentadienyl titanium allyl methoxide,pentamethylcyclopentadienyl titanium allyl methoxide, cyclopentadienyltitanium allyl ethoxide, methylcyclopenadienyl titanium allyl ethoxide,ethylcyclopentadienyl titanium allyl ethoxide, t-butylcyclopentadienyltitanium allyl ethoxide, n-butylcyclopentadienyl titanium allylethoxide, pentamethylcyclopentadienyl titanium allyl ethoxide,cyclopentadienyl titanium allyl isopropoxide, methylcyclopentadienyltitanium allyl isopropoxide, ethylcyclopentadienyl titanium allylisopropoxide, t-butylcyclopentadienyl titanium allyl isopropoxide,n-butylcyclopentadienyl titanium allyl isopropoxide,pentamethylcyclopentadienyl titanium allyl isopropoxide,cyclopentadienyl titanium allyl phenoxide, methylcyclopentadienyltitanium allyl phenoxide, ethylcyclopentadienyl titanium allylphenoxide, t-butylcyclopentadienyl titanium allyl phenoxide,n-butylcyclopentadienyl titanium allyl phenoxide,pentamethylcyclopentadienyl titanium allyl phenoxide, cyclopentadienyltitanium (2-methylallyl) chloride, methylcyclopentadienyl titanium(2-methylallyl) chloride, ethylcyclopentadienyl titanium (2-methylallyl)chloride, t-butylcyclopentadienyl titanium (2-methylallyl) chloride,pentamethylcyclopentadienyl titanium (2-methylallyl) chloride,n-butylcyclopentadienyl titanium (2-methylallyl) chloride,pentamethylcyclopentadienyl titanium (2-methylallyl) chloride,cyclopentadienyl titanium (2-methylallyl) bromide,methylcyclopentadienyl titanium (2-methylallyl) bromide,ethylcyclopentadienyl titanium (2-methylallyl) bromide,t-butylcyclopentadienyl titanium (2-methylallyl) bromide,n-butylcyclopentadienyl titanium (2-methylallyl) bromide,pentamethylcyclopentadienyl titanium (2-methylallyl) bromide,cyclopentadienyl titanium (2-methylallyl) methoxide,methylcyclopentadienyl titanium (2-methylallyl) methoxide,ethylcyclopentadienyl titanium (2-methylallyl) methoxide,butylcyclopentadienyl titanium (2-methylallyl) methoxide,pentamethylcyclopentadienyl titanium (2-methylallyl) methoxide,cyclopentadienyl titanium (2-methylallyl) ethoxide,methylcyclopentadienyl titanium (2-methylallyl) ethoxide,ethylcyclopentadienyl titanium (2-methylallyl) ethoxide,t-butylcyclopentadienyl titanium (2-methylallyl) ethoxide,n-butylcyclopentadienyl titanium (2-methylallyl) ethoxide,pentamethylcyclopentadienyl)titanium (2-methylallyl) ethoxide,cyclopentadienyl titanium (2-methylallyl) isopropoxide,methylcyclopentadienyl titanium (2-methylallyl) isopropoxide,ethylcyclopentadienyl titanium (2-methylallyl) isopropoxide,t-butylcyclopentadienyl titanium (2-methylallyl) isopropoxide,n-butylcyclopentadienyl titanium (2-methylallyl) isopropoxide,pentamethylcyclopentadienyl titanium (2-methylallyl) isopropoxide,cyclopentadienyl titanium (2-methylallyl) phenoxide,methylcyclopentadienyl titanium (2-methylallyl) phenoxide,ethylcyclopentadienyl titanium (2-methylallyl) phenoxide,t-butylcyclopentadienyl titanium (2-methylallyl) phenoxide,n-butylcyclopentadienyl titanium (2-methylallyl) phenoxide,pentamethylcyclopentadienyl titanium (2-methylallyl) phenoxide,cyclopentadienyl titanium (2-dimethylaminobenzyl) chloride,methylcyclopentadienyl titanium (2-dimethylaminobenzyl) chloride,ethylcylopentadienyl titanium (2-dimethylaminobenzyl) chloride,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) chloride,n-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) chloride,pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl) chloride,cyclopentadienyl titanium (2-dimethylaminobenzyl) bromide,methylcyclopentadienyl titanium (2-dimethylaminobenzyl) bromide,ethylcyclopentadienyl titanium (2-dimethylaminobenzyl) bromide,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) bromide,n-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) bromide,pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl) bromide,cyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,methylcyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,ethylcyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,cyclopentadienyl titanium (2-dimethylaminobenzyl) ethoxide,methylcyclopentadienyl titanium (2-dimethylaminobenzyl) ethoxide,ethylcyclopentadienyl titanium (2-dimethylaminobenyl) ethoxide,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) ethoxide,n-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) ethoxide,pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl) ethoxide,cyclopentadienyl titanium (2-dimethylaminobenzyl) isopropoxide,methylcyclopentadienyl titanium (2-dimethlaminobenzyl) isopropoxide,ethylcyclopentadienyl titanium (2-dimethylaminobenzyl) isopropoxide,n-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) isopropoxide,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) isopropoxide,pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl)isopropoxide, cyclopentadienyl titanium (2-dimethylaminobenzyl)phenoxide, methylcyclopentadienyl titanium (2-dimethylaminobenzyl)phenoxide, ethylcyclopentadienyl titanium (2-dimethylaminobenzyl)phenoxide, butylcyclopentadienyl titanium (2-dimethylaminobenzyl)phenoxide, pentamethycyclopentadienyl titanium (2-dimethylaminobenzyl)phenoxide, cyclopentadienyl titanium (2-dimethylaminomethylphenyl)chloride, methylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)chloride, ethylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)chloride, t-butylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)chloride, n-butylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)chloride, pentamethylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) chloride, cyclopentadienyl titanium(2-dimethylaminomethylphenyl) bromide, methylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) bromide, ethylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) bromide, t-butylcyclopentadienyl titaniumdimethylaminomethylphenyl) bromide, n-butylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) bromide, pentamethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) bromide, cyclopentadienyltitanium (2-dimethylaminomethylphenyl) methoxide, methylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) methoxide, ethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) methoxide,n-butylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)methoxide, t-butylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) methoxide, pentamethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) methoxide, cyclopentadienyltitanium (2-dimethylaminomethylphenyl) ethoxide, methylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) ethoxide, ethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) ethoxide, n-butylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) ethoxide, t-butylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) ethoxide,pentamethylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)ethoxide, cyclopentadienyl titanium (2-dimethylaminomethylphenyl)isopropoxide, methylcyclopentadienyl titanium(2-diethylaminomethylphenyl) isopropoxide, ethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) isopropoxide,n-butylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)isopropoxide, t-butylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) isopropoxide, pentamethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) isopropoxide, cyclopentadienyltitanium (2-dimethylaminomethylphenyl) phenoxide, methylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) phenoxide, ethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) phenoxide,n-butylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) phenoxide,t-butylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) phenoxide,pentamethylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)phenoxide, cyclopentadienyl titanium allyl dimethylamide,methylcyclopentadienyl titanium allyl dimethylamide,ethylcyclopentadienyl titanium allyldimethylamide, butylcyclopentadienyltitanium allyl dimethylamide, pentamethylcyclopentadienyl titanium allyldimethylamide, cyclopentadienyl titanium allyl diethylamide,methylcyclopentadienyl titanium allyl diethylamide,ethylcyclopentadienyl titanium allyl diethylamide,n-butylcyclopentadienyl titanium allyl diethylamide,t-butylcyclopentadienyl titanium allyl diethylamide,pentamethylcyclopentadienyl titanium allyl diethylamide,cyclopentadienyl titanium allyl (di-t-butylamide),methylcyclopentadienyl titanium allyl (di-t-butylamie),ethylcyclopentadienyl titanium allyl (di-t-butylamide),butylcyclopentadienyl titanium allyl (di-t-butylamide),pentamethylcyclopentadienyl titanium allyl (di-t-butylamide),cyclopentadienyl titanium diallyl, cyclopentadienyl titanium(2-methylallyl) dimethylamide, methylcyclopentadienyl titanium(2-methylallyl) dimethylamide, ethylcyclopentadienyl titanium(2-methylallyl) dimethylamide, butylcyclopentadienyl titanium(2-methylallyl) dimethylamide, pentamethylcyclopentadienyl titanium(2-methylallyl) dimethylamide, cyclopentadienyl titanium (2-methylallyl)diethylamide, methylcyclopentadienyl titanium (2-methylallyl)diethylamide, ethylcyclopentadienyl titanium (2-methylallyl)diethylamide, butylcyclopentadienyl titanium (2-methylallyl)diethylamide, pentamethylcyclopentadienyl titanium (2-methylallyl)diethylamide, cyclopentadienyl titanium (2-methylallyl)(di-t-butylamide), methylcyclopentadienyl titanium (2-methylallyl)(di-t-butylamide), ethylcyclopentadienyl titanium (2-methylallyl)methoxide, butylcyclopentadienyl titanium (2-methylallyl)(di-t-butylamide), pentamethylcyclopentadienyl titanium (2-methylallyl)(di-t-butylamide), cyclopentadienyl titanium bis-(2-methylallyl),cyclopentadienyl titanium (2-dimethylaminobenzyl) dimethylamide,methylcyclopentadienyl titanium (2-dimethylaminobenzyl) dimethylamide,ethylcyclopentadienyl titanium (2-dimethylaminobenzyl) dimethylamide,n-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) dimethylamide,t-butylcyclopentadienyl titanium (2-dimethylaminobenzyl) dimethylamide,pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl)dimethylamide, cyclopentadienyl titanium (2-dimethylaminobenzyl)diethylamide, methylcyclopentadienyl titanium (2-dimethylaminobenzyl)diethylamide, ethylcyclopentadienyl titanium (2-dimethylaminobenzyl)diethylamide, butylcyclopentadienyl titanium (2-dimethylaminobenzyl)diethylamide, pentamethylcyclopentadienyl titanium(2-dimethylaminobenzyl) diethylamide, cyclopentadienyl titanium(2-dimethylaminobenzyl) methoxide, methylcyclopentadienyl titanium(2-dimethylaminobenzyl) (di-t-butylamide), ethylcyclpentadienyl titanium(2-dimethylaminobenzyl) (di-t-butylamide), butylcyclopentadienyltitanium (2-dimethylaminobenzyl) (di-t-butylamide),pentamethylcyclopentadienyl titanium (2-dimethylaminobenzyl) methoxide,cyclopentadienyl titanium bis-(2-dimethylaminobenzyl), cyclopentadienyltitanium (2-dimethylaminomethylphenyl) dimethylamide,methylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)dimethylamide, ethylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) dimethylamide, butylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) dimethylamide,pentamethylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)dimethylamide, cyclopentadienyl titanium (2-dimethylaminomethylphenyl)diethylamide, methylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) diethylamide, ethylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) diethylamide,butylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)diethylamide, pentamethylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) diethylamide, cyclopentadienyl titanium(2-dimethylaminomethylphenyl) (di-t-butylamide), methylcyclopentadienyltitanium (2-dimethylaminomethylphenyl) (di-t-butylamide),ethylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)(di-t-butylamide), butylcyclopentadienyl titanium(2-dimethylaminomethylphenyl) (di-t-butylamide),pentamethylcyclopentadienyl titanium (2-dimethylaminomethylphenyl)(di-t-butylamide), cyclopentadienyl titaniumbis-(2-dimethylaminomethylphenyl), cyclopentadienyl titanium methyl2-dimethylaminobenzyl, cyclopentadienyl titanium benzyl2-dimethylaminobenzyl, cyclopentadienyl titanium trimethylsilylmethyl2-(dimethylamino)benzyl, methylcyclopentadienyl titanium methyl2-dimethylaminobenzyl, methylcyclopentadienyl titanium benzyl2-dimethylaminobenzyl, methylcyclopentadienyl titaniumtrimethylsilylmethyl 2-(dimethylamino)benzyl,pentamethylcyclopentadienyl titanium methyl 2-dimethylaminobenzyl,pentamethylcyclopentadienyl titanium benzyl 2-dimethylaminobenzyl,pentamethylcyclopentadienyl titanium trimethylsilylmethyl2-(dimethylamino)benzyl, cyclopentadienyl zirconium allyl chloride,methylcyclopentadienyl zirconium allyl chloride, ethylcyclopentadienylzirconium allyl chloride, t-butylcyclopentadienyl zirconium allylchloride, pentamethylcyclopentadienyl zirconium allyl chloride,cyclopentadienyl zirconium allyl bromide, methylcyclopentadienylzirconium allyl bromide, ethylcyclopentadienyl zirconium allyl bromide,n-butylcyclopentadienyl zirconium allyl bromide, t-butylcyclopentadienylzirconium allyl bromide, pentamethylcyclopentadienyl zirconium allylbromide, cyclopentadienyl zirconium allyl methoxide,methylcyclopentadienyl zirconium allyl methoxide, ethylcyclopentadienylzirconium allyl methoxide, n-butylcyclopentadienyl zirconium allylmethoxide, t-butylcyclopentadienyl zirconium allyl methoxide,pentamethylcyclopentadienyl zirconium allyl methoxide, cyclopentadienylzirconium allyl ethoxide, methylcyclopentadienyl zirconium allylethoxide, ethylcyclopentadienyl zirconium allyl ethoxide,n-butylcyclopentadienyl zirconium allyl ethoxide,t-butylcyclopentadienyl zirconium allyl ethoxide,pentamethylcyclopentadienyl zirconium allyl ethoxide, cyclopentadienylzirconium allyl isopropoxide, methylcyclopentadienyl zironium allylisopropoxide, ethylcyclopentadienyl zirconium allyl isopropoxide,n-butylcyclopentadienyl zirconium allyl isopropoxide,t-butylcyclopentadienyl zirconium allyl isopropoxide,pentamethylcyclopentadienyl zirconium allyl isopropoxide,cyclopentadienyl zirconium allyl phenoxide, methylcyclopentadienylzirconium allyl phenoxide, ethylcyclopentadienyl zirconium allylphenoxide, n-butylcyclopentadienyl zirconium allyl phenoxide,t-butylcyclopentadienyl zirconium allyl phenoxide,pentamethylcyclopentadienyl zirconium allyl phenoxide, cyclopentadienylzirconium (2-methylallyl) chloride, methylcyclopentadienyl zirconium(2-methylallyl) chloride, ethylcyclopentadienyl zirconium(2-methylallyl) chloride, n-butylcyclopentadienyl zirconium(2-methylallyl) chloride, t-butylcyclopentadienyl zirconium(2-methylallyl) chloride, pentamethylcyclopentadienyl zirconium(2-methylallyl) chloride, cyclopentadienyl zirconium (2-methylallyl)bromide, methylcyclopentadienyl zirconium (2-methylallyl) bromide,ethylcyclopentadienyl zirconium (2-methylallyl) bromide,n-butylcyclopentadienyl zirconium (2-methylallyl) bromide,t-butylcyclopentadienyl zirconium (2-methylallyl) bromide,pentamethylcyclopentadienyl zirconium (2-methylallyl) bromide,cyclopentdienyl zirconium (2-methylallyl) methoxide,methylcyclopentadienyl zirconium (2-methylallyl) methoxide,ethylcyclopentadienyl zirconium (2-methylallyl) methoxide,butylcyclopentadienyl zirconium (2-methylallyl) methoxide,pentamethylcyclopentadienyl zirconium (2-methylallyl) methoxide,cyclopentadienyl zirconium (2-methylallyl) ethoxide,methylcyclopentadienyl zirconium (2-methylallyl) ethoxide,ethylcyclopentadienyl zirconium (2-methylallyl) ethoxide,butylcyclopentadienyl zirconium (2-methylallyl) ethoxide,pentamethylcyclopentadienyl zirconium (2-methylallyl) ethoxide,cyclopentadienyl zirconium (2-methylallyl) isopropoxide,methylcyclopentadienyl zirconium (2-methylallyl) isopropoxide,ethylcyclopentadienyl zirconium (2-methylallyl) isopropoxide,n-butylcyclopentadienyl zirconium (2-methylallyl) isopropoxide,t-butylcyclopentadienyl zirconium (2-methylallyl) isopropoxide,pentamethylcyclopentadienyl zirconium (2-methylallyl) isopropoxide,cyclopentadienyl zirconium (2-methylallyl) phenoxide,methylcyclopentadienyl zirconium (2-methylallyl) phenoxide,ethylcyclopentadieyl zirconium (2-methylallyl) phenoxide,n-butylcyclopentadienyl zirconium (2-methylallyl) phenoxide,t-butylcyclopentadienyl zirconium (2-methylallyl) phenoxide,pentamethylcyclopentadienyl zirconium (2-methylallyl) phenoxide,cyclopentadienyl zirconium (2-dimethylaminobenzyl) chloride,methylcyclopentadienyl zirconium (2-dimethylaminobenzyl) chloride,ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) chloride,n-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) chloride,t-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) chloride,pentamethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) chloride,cyclopentadienyl zirconium (2-dimethylaminobenzyl) bromide,methylcyclopentadienyl zirconium (2-dimethylaminobenzyl) bromide,ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) bromide,n-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) bromide,t-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) bromide,pentamethylcyclpentadienyl zirconium (2-dimethylaminobenzyl) bromide,cyclopentadienyl zirconium (2-dimethylaminobenzyl) methoxide,methylcyclopentadienyl zirconium (2-dimethylaminobenzyl) methoxide,ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) methoxide,butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) methoxide,pentamethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) methoxide,cyclopentadienyl zirconium (2-dimethylaminobenzyl) ethoxide,methylcyclopentadienyl zirconium (2-dimethylaminobenzyl) ethoxide,ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) ethoxide,butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) ethoxide,pentamethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) ethoxide,cyclopentadienyl zirconium (2-dimethylaminobenzyl) isopropoxide,methylcyclopentadienyl zirconium (2-dimethylaminobenzyl) isopropoxide,ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) isopropoxide,butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) isopropoxide,pentamethylcyclopentadienyl zirconium (2-dimethylaminobenzyl)isopropoxide, cyclopentadienyl zirconium (2-dimethylaminobenzyl)phenoxide, methylcyclopentadienyl zirconium (2-dimethylaminobenzyl)phenoxide, ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl)phenoxide, butylcylopentadienyl zirconium (2-dimethylaminobenzyl)phenoxide, pentamethylcyclopentadienyl zirconium (2-dimethylaminobenzyl)phenoxide, cyclopentadienyl zirconium (2-dimethylaminomethylphenyl)chloride, methylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)chloride, ethylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)chloride, butylcyclopentadienyl zirconium (2-dimethylminomethylphenyl)chloride, pentamethylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) chloride, cyclopentadienyl zirconium(2-dimethylaminomethylphenyl) bromide, methylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) bromide, ethylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) bromide, butylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) bromide, pentamethylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) bromide, cyclopentadienylzirconium (2-dimethylaminomethylphenyl) methoxide,methylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)methoxide, ethylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)methoxide, butylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl) methoxide, pentamethylcycloentadienylzirconium (2-dimethylaminomethylphenyl) methoxide, cyclopentadienylzirconium (2 -dimethylaminomethylphenyl) ethoxide,methylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl) ethoxide,ethylcyclopentadienyl zirconium (2-dimethylaminomethyphenyl) ethoxide,t-butylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)ethoxide, n-butylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) ethoxide, pentamethylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) ethoxide, cyclopentadienylzirconium (2-dimethylaminomethylphenyl) isopropoxide,methylcyclopentaienyl zirconium (2-dimethylaminomethylphenyl)isopropoxide, ethylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) isopropoxide, n-butylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) isopropoxide,t-butylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)isopropoxide, pentamethylcyclopentadienyl zirconium(2-diethylaminomethylphenyl) isopropoxide, cyclopentadienyl zirconium(2-dimethylaminomethylphenyl) phenoxide, methylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) phenoxide, ethylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) phenoxide,n-butylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)phenoxide, t-butylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) phenoxide, pentamethylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) phenoxide, cyclopentadienylzirconium allyl dimethylamide, methylcyclopentadienyl zirconium allyldimethylamide, ethylcyclopentadienyl zirconium allyl dimethylamide,n-butylcyclopentadienyl zirconium allyl dimethylamide,t-butylcyclopentadienyl zirconium allyl dimethylamide,pentamethylcyclopentadienyl zirconium allyl dimethylamide,cyclopentadienyl zirconium allyl diethylamide, methylcyclopentadienylzirconium allyl diethylamde, ethylcyclopentadienyl zirconium allyldiethylamide, n-butylcyclopentadienyl zirconium allyl diethylamide,t-butylcyclopentadienyl zirconium allyl diethylamide,pentamethylcyclopentadienyl zirconium allyl diethylamide,cyclopentadienyl zirconium allyl (di-t-butylamide),methylcyclopentadienyl zirconium allyl (di-t-butylamide),ethylcyclopentadienyl zirconium allyl (di-t-butylamide),n-butylcyclopentadienyl zirconium allyl (di-t-butylamide),t-butylcyclopentadienyl zirconium allyl (di-t-butylamide),pentamethylcyclopentadienyl zirconium allyl (di-t-butylamide),cyclopentadienyl zirconium diallyl, cyclopentadienyl zirconium(2-methylallyl) dimethylamide, methylcyclopentadienyl zirconium(2-methylallyl) dimethylamide, ethylcyclopentadienyl zirconium(2-methylallyl) dimethylamide, n-butylcyclopentadienyl zirconium(2-methylallyl) dimethylamide t-butylcyclopentadienyl zirconium(2-methylallyl) dimethylamide, pentamethylcyclopentadienyl zirconium(2-methylallyl) dimethylamide, cyclopentadienyl zirconium(2-methylallyl) diethylamide, methylcyclopentadienyl zirconium(2-methylallyl) diethylamide, ethylcyclopentadienyl zirconium(2-methylallyl) diethylamide, butylcyclopentadienyl zirconium(2-methylallyl) diethylamide, pentamethylcyclopentadienyl zirconium(2-methylallyl) diethylamide, cyclopentadienyl zirconium (2-methylallyl)(di-t-butylamide), methylcyclopentadienyl zirconium (2-methylallyl)(di-t-butylamide), methylcyclopentadienyl zirconium (2-methylallyl)methoxide, butylcyclopentadienyl zirconium (2-methylallyl)(di-t-butylamide), pentamethylcyclopentadienyl zirconium (2-methylallyl)(di-t-butylamide), cyclopentadienyl zirconium bis-(2-methylallyl),cyclopentdienyl zirconium (2-dimethylaminobenzyl) dimethylamide,methylcyclopentadienyl zirconium (2-dimethylaminobenzyl) dimethylamide,ethylcyclopentadienyl zirconium (2-dimethylaminobenzyl) dimethylamide,n-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) dimethylamide,t-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl) dimethylamide,pentamethylcyclopentadienyl zirconium (2-dimethylaminobenzyl)dimethylamide, cyclopentadienyl zirconium (2-dimethylaminobenzyl)diethylamide, methylcyclopentadienyl zirconium (2-dimethylaminobenzyl)diethylamide, ethylcyclopentadienyl zirconum (2-dimethylaminobenzyl)diethylamide, n-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl)diethylamide, t-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl)diethylamide, pentamethylcyclopentadienyl zirconium(2-dimethylaminobenzyl) diethylamide, cyclopentadienyl zirconium(2-dimethylaminobenzyl) methoxide, methylcyclopentadienyl zirconium(2-dimethylaminobenzyl) (di-t-butylamide), ethylcyclopentadienylzirconium (2-dimethylaminobenzyl) (di-t-butylamide ),n-butylcyclopentadienyl zirconium (2-dimethylaminobenzyl)(di-t-butylamide), t-butylcyclopentadienyl zirconium(2-dimethylaminobenzyl) (di-t-butylamide), pentamethylcyclopentadienylzirconium (2-dimethylaminobenzyl) methoxide, cyclopentadienyl zirconiumbis-(2-dimethylaminobenzyl), cyclopentadienyl zirconium(2-dimethylaminomethylphenyl) dimethylamide, methylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) dimethylamide,ethylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)dimethylamide, butylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) dimethylamide, pentamethylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) dimethylamide, cyclopentadienylzirconium (2-diethylaminomethylphenyl) diethylamide,methylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)diethylamide, ethylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) diethylamide, n-butylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) diethylamide,t-butylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)diethylamide, pentamethylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) diethylamide, cyclopentadienyl zirconium(2-dimethylaminomethylphenyl) (di-t-butylamide), methylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) (di-t-butylamide),ethylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)(di-t-butylamide), n-butylcyclopentadienyl zirconium(2-dimethylaminomethylphenyl) (di-t-butylamide), t-butylcyclopentadienylzirconium (2-dimethylaminomethylphenyl) (di-t-butylamide),pentamethylcyclopentadienyl zirconium (2-dimethylaminomethylphenyl)(di-t-butylamide), cyclopentadenyl zirconiumbis-(2-dimethylaminomethylphenyl), cyclopentadienyl zirconium methyl2-dimethylaminobenzyl, cyclopentadienyl zirconium benzyl2-dimethylaminobenzyl, cyclopentadienyl zirconium trimethylsilylmethyl2-(dimethylamino)benzyl, methylcyclopentadienyl zirconium methyl2-dimethylaminobenzyl, methylcyclopentadienyl zirconium benzyl2-dimethylaminobenzyl, methylcyclopentadienyl zirconiumtrimethylsilylmethyl 2-(dimethylamino)benzyl,pentamethylcyclopentadienyl zirconium methyl 2-dimethylaminobenzyl,pentamethylcyclopentadienyl zirconium benzyl 2-dimethylaminobenzyl,pentamethylcyclopentadienyl zirconium trimethylsilylmethyl2-(dimethylamino)benzyl, cyclopentadienyl hafnium allyl chloride,methylcyclopentadienyl hafnium allyl chloride, ethylcyclopentadienylhafnium allyl chloride, n-butylcyclopentadienyl hafnium allyl chloride,t-butylcyclopentadienyl hafnium allyl chloride,pentamethylcyclopentadienyl hafnium allyl chloride, cyclopentadienylhafnium allyl bromide, methylcyclopentadienyl hafnium allyl bromide,ethylcyclopentadienyl hafnium allyl bromide, n-butylcyclopentadienylhafnium allyl bromide, t-butylcyclopentadienyl hafnium allyl bromide,pentamethylcyclopentadienyl hafnium allyl bromide, cyclopentadienylhafnium allyl methoxide, methylcyclpentadienyl hafnium allyl methoxide,ethylcyclopentadienyl hafnium allyl methoxide, n-butylcyclopentadienylhafnium allyl methoxide, t-butylcyclopentadienyl hafnium allylmethoxide, pentamethylcyclopentadienyl hafnium allyl methoxide,cyclopentadienyl hafnium allyl ethoxide, methylcyclopentadienyl hafniumallyl ethoxide, ethylcyclopentadienyl hafnium allyl ethoxide,n-butylcyclopentadienyl hafnium allyl ethoxide, t-butylcyclopentadienylhafnium allyl ethoxide, pentamethylcyclopentadienyl hafnium allylethoxide, cyclopentadienyl hafnium allyl isopropoxide,methylcyclopentadienyl hafnium allyl isopropoxide, ethylcyclopentadienylhafnium allyl isopropoxide, n-butylcyclopentadienyl hafnium allylisopropoxide, t-butylcyclopentadienyl hafnium allyl isopropoxide,pentamethylcyclopentadienyl hafnium allyl isopropoxide, cyclopentadienylhafnium allyl phenoxide, methylcyclopentadienyl hafnium allyl phenoxide,ethylcyclopentadienyl hafnium allyl phenoxide, n-butylcyclopentadienylhafnium allyl phenoxide, t-butylcyclopentadienyl hafnium allylphenoxide, pentamethylcyclopentadienyl hafnium allyl phenoxide,cyclopentadienyl hafnium (2-methylallyl) chloride,methylcyclopentadienyl hafnium (2-methylallyl) chloride,ethylcyclopentadienyl hafnium (2-methylallyl) chloride,n-butylcyclopentadienyl hafnium (2-methylallyl) chloride,t-butylcyclopentadienyl hafnium (2-methylallyl) chloride,pentamethylcyclopentadienyl hafnium (2-methylallyl) chloride,cyclopentadienyl hafnium (2-methylallyl) bromide, methylcyclopentadienylhafnium (2-methylallyl) bromide, ethylcyclopentadienyl hafnium(2-methylallyl) bromide, n-butylcyclopentadienyl hafnium (2-methylallyl)bromide, t-butylcyclopentadienyl hafnium (2-methylallyl) bromide,pentamethylcyclopentadienyl hafnium (2-methylallyl) bromide,cyclopentadienyl hafnium (2-methylallyl) methoxide,methylcyclopentadieyl hafnium (2-methylallyl) methoxide,ethylcyclopentadienyl hafnium (2-methylallyl) methoxide,n-butylcyclopentadienyl hafnium (2-methylallyl) methoxide,t-butylcyclopentadienyl hafnium (2-methylallyl) methoxide,pentamethylcyclopentadienyl hafnium (2-methylallyl) methoxide,cyclopentadienyl hafnium (2-methylallyl)ethoxide, methylcyclopentadienylhafnium (2-methylallyl) ethoxide, ethylcyclopentadienyl hafnium(2-methylallyl) ethoxide, t-butylcyclopentadienyl hafnium(2-methylallyl) ethoxide, t-butylcyclopentadienyl hafnium(2-methylallyl) ethoxide, pentamethylcyclopentadienyl hafnium(2-methylallyl) ethoxide, cyclopentadienl hafnium (2-methylallyl)isopropoxide, methylcyclopentadienyl hafnium (2-methylallyl)isopropoxide, ethylcyclopentadienyl hafnium (2-methylallyl)isopropoxide, n-butylcyclopentadienyl hafnium (2-methylallyl)isopropoxide, t-butylcyclopentadienyl hafnium (2-methylallyl)isopropoxide, pentamethylcyclopentadienyl hafnium (2-methylallyl)isopropoxide, cyclopentadienyl hafnium (2-methylallyl) phenoxide,methylcyclopentadienyl hafnium (2-methylallyl) phenoxide,ethylcyclopentadienyl hafnium (2-methylallyl) phenoxide,n-butylcyclopentadienyl hafnium (2-methylallyl) phenoxide,t-butylcyclopentadienyl hafnium (2-methylallyl) phenoxide,pentamethylcyclopentadienyl hafnium (2-methylallyl) phenoxide,cyclopentadienyl hafnium (2-dimethylaminobenzyl) chloride,methylcyclopentadienyl hafnium (2-dimethylaminobenzyl) chloride,ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) chloride,n-butylyclopentadienyl hafnium (2-dimethylaminobenzyl) chloride,t-butylyclopentadienyl hafnium (2-dimethylaminobenzyl) chloride,pentamethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) chloride,cyclopentadienyl hafnium (2-dimethylaminobenzyl) bromide,methylcyclopentadienyl hafnium (2-dimethylaminobenzyl) bromide,ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) bromide,n-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) bromide,t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) bromidepentamethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) bromide,cyclopentadienyl hafnium (2-dimethylaminobenzyl) methoxide,methylcyclopentadienyl hafnium (2-dimethylaminobenzyl) methoxide,ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) methoxide,t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) methoxide,t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) methoxide,pentamethylcyclopentadienyl hafnium (2 -dimethylaminobenzyl) methoxide,cyclopentadienyl hafnium (2-dimethylaminobenzyl) ethoxide,methylcyclopentadienyl hafnium (2-dimethylaminobenzyl) ethoxide,ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) ethoxide,n-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) ethoxide,t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) ethoxide,pentamethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) ethoxide,cyclopentadienyl hafnium (2-dimethylaminobenzyl) isopropoxide,methylcyclopentadienyl hafnium (2-dimethylaminobenzyl) isopropoxide,ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl)isopropoxide,n-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) isopropoxide,t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) isopropoxide,pentamethylcyclopentadienyl hafnium (2-dimethylaminobenzyl)isopropoxide, cyclopentadienyl hafnium (2-dimethylaminobenzyl)phenoxide, methylcyclopentadienyl hafnium (2-dimetylaminobenzyl)phenoxide, ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl)phenoxide, n-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl)phenoxide, t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl)phenoxide, pentamethylcyclopentadienyl hafnium (2-dimethylaminobenzyl)phenoxide, cyclopentadienyl hafnium (2-dimethylaminomethylphenyl)chloride, methylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)chloride, ethylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)chloride, n-butylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)chloride, t-butylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)chloride, pentamethylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) chloride, cyclopentadienyl hafnium(2-dimethylaminomethylphenyl) bromide, methylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) bromide, ethylcyclopentadienyl hafium(2-dimethylaminomethylphenyl) bromide, t-butylcyclopentadienyl hafnium(2 -dimethylaminomethylphenyl) bromide, pentamethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) bromide, cyclopentadienyl hafnium(2-dimethylaminomethylphenyl) methoxide, methylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) methoxide, ethylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) methoxide, n-butylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) methoxide, t-butylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) methoxide, pentamethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) methoxide, cyclopentadienylhafnium (2 -dimethylaminomethylphenyl) ethoxide, methylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) ethoxide, ethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) ethoxide, n-butylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) ethoxide t-butylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) ethoxide,pentamethylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)ethoxide, cyclopentadienyl hafnium (2-dimethylaminomethylphenyl)isopropoxide, methylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) isopropoxide, ethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) isopropoxide,n-butylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)isopropoxide, t-butylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) isopropoxide, pentamethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) isopropoxide, cyclopentadenylhafnium (2-dimethylaminomethylphenyl) phenoxide, methylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) phenoxide, ethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) phenoxide, n-butylcyclopentadienylhafnium (2-dimethylaminomethylphenyl phenoxide, t-butylcyclopentadienylhafnium (2-dimethylaminomethylphenyl phenoxide,pentamethylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)phenoxide, cyclopentadienyl hafnium allyl dimethylamide,methylcyclopentadienyl hafnium allyl dimethylamide,ethylcyclopentadienyl hafnium allyl dimethylamide,t-butylcyclopentadienyl hafnium allyl dimethylamide,pentamethylcyclopentadienyl hafnium allyl dimethylamide,cyclopentadienyl hafnium allyl diethylamide, methylcyclopentadienylhafnium allyl diethylamide, ethylcyclopentadienyl hafnium allyldiethylamide, butylcyclopentadienyl hafnium allyl diethylamide,pentamethylcyclopentadienyl hafnium allyl diethylamide, cyclopentadienylhafnium allyl (di-t-butylamide), methylcyclopentadienyl hafnium allyl(di-t-butylamide), ethylcyclopentadienyl hafnium allyl(di-t-butylamide), butylcyclopentadienyl hafnium allyl(di-t-butylamide), pentamethylcyclopentadienyl hafnium allyl(di-t-butylamide), cyclopentadienyl hafnium diallyl, cyclopentadienylhafnium (2-methylallyl) dimethylamide, methylcyclopentadienyl hafnium(2-methylallyl) dimethylamide, ethylcyclopentadienyl hafnium(2-methylallyl) dimethylamide, n-butylcyclopentadienyl hafnium(2-methylallyl) dimethylamide, t-butylcyclopentadienyl hafnium(2-methylallyl) dimethylamide, pentamethylcyclopentadienyl hafnium(2-methylallyl) dimethylamide, cyclopentadienyl hafnium (2-methylallyl)dethylamide, methylcyclopentadienyl hafnium (2-methylallyl)diethylamide, ethylcyclopentadienyl hafnium (2-methylallyl)diethylamide, n-butylcyclopentadienyl hafnium (2-methylallyl)diethylamide, t-butylcyclopentadienyl hafnium (2-methylallyl)diethylamide, pentamethylcyclopentadienyl hafnium (2-methylallyl)diethylamide, cyclopentadienyl hafnium (2-methylallyl)(di-t-butylamide), methylcyclopentadienyl hafnium (2-methylallyl)(di-t-butylamide), ethylcyclopentadienyl hafnium (2-methylallyl)methoxide, n-butylcyclopentadienyl hafnium (2-methylallyl)(di-t-butylamide), t-butylcyclopentadienyl hafnium (2-methylallyl)(di-t-butylamide), pentamethylcyclopentadienyl hafnium (2-methylallyl)(di-t-butylamide), cyclopentadienyl hafnium bis-(2-methylallyl),cyclopentadienyl hafnium (2-dimethylaminobenzyl) dimethylamide,methylcyclopentadienyl hafnium (2-dimethylaminobenzyl) dimethylamide,ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl) dimethylamide,n-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) dimethylamide,t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl) dimethylamide,pentamethylcyclopentadienyl hafnium (2-dimethylaminobenzyl)dimethylamide, cyclopentadienyl hafnium (2-dimethylaminobenzyl)diethylamide, methylcyclopentadienyl hafnium (2-dimethylaminobenzyl)diethylamide, ethylcyclopentadienyl hafnium (2-dimethylaminobenzyl)diethylamide, n-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl)diethylamide, t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl)diethylamide, pentamethylcyclopentadienyl hafnium(2-dimethylaminobenzyl) diethylamide, cyclopentadienyl hafnium(2-dimethylaminobenzyl) methoxide, methylcyclopentadienyl hafnium(2-dimethylaminobenzyl) (di-t-butylamide), ethylcyclopentadienyl hafnium(2-dimethylaminobenzyl) (di-t-butylamide), n-butylcyclopentadienylhafnium (2-dimethylaminobenzyl) (di-t-butylamide),t-butylcyclopentadienyl hafnium (2-dimethylaminobenzyl)(di-t-butylamide), pentamethylcyclopentadienyl hafnium(2-dimethylaminobenzyl) methoxide, cyclopentadienyl hafniumbis-(2-dimethylaminobenzyl), cyclopentadienyl hafnium(2-dimethylaminomethylphenyl) dimethylamide, methylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) dimethylamide,ethylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)dimethylamide, n-butyl cyclopentadienyl hafnium(2-dimethylaminomethylphenyl) dimethylamide, t-butylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) dimethylamide,pentamethylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)dimethylamide, cyclopentadienyl hafnium (2- dimethylaminomethylphenyl)diethylamide, methylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) diethylamide, ethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl)diethylamide,n-butylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) diethylamide, t-butylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) diethylamide,pentamethylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)diethylamide, cyclopentadienyl hafnium (2-dimethylaminomethylphenyl)(di-t-butylamide), methylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) (di-t-butylamide), ethylcyclopentadienylhafnium (2-dimethylaminomethylphenyl) (di-t-butylamide),n-butylcyclopentadienyl hafnium (2-dimethylaminomethylphenyl)(di-t-butylamide), t-butylcyclopentadienyl hafnium(2-dimethylaminomethylphenyl) (di-t-butylamide),pentamethylcyclopentadienyl hafnium 2-dimethylaminomethylphenyl)(di-t-butylamide), cyclopentadienyl hafniumbis-(2-dimethylaminomethylphenyl), cyclopentadienyl hafnium methyl2-dimethylaminobenzyl, cyclopentadienyl hafnium benzyl2-dimethylaminobenzyl, cyclopentadienyl hafnium trimethylsilylmethyl2-(dimethylamino)benzyl, methylcyclopentadienyl hafnium methyl2-dimethylaminobenzyl, methylcyclopentadienyl hafnium benzyl2-dimethylaminobenzyl, methylcyclopentadienyl hafniumtrimethylsilylmethyl 2-(dimethylamino)benzyl,pentamethylcyclopentadienyl hafnium methyl 2-dimethylaminobenzyl,pentamethylcyclopentadienyl hafnium benzyl 2-dimethylaminobenzyl,pentamethylcyclopentadienyl hafnium trimethylsilylmethyl2-(dimethylamino)benzyl.

Illustrative cyclic complexes, A₃, that may be employed in the practiceof the present invention include:(tert-butylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl titanium, (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium,(tert-butylamido)(tetramethyl-η⁵ -cyclopentadienyl)-1,2-ethanediyl allyltitanium, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl 2-(dimethylamino)benzyltitanium,(methylamido)(η⁵ -cyclopentadienyl)-1,2-ethanediyl2-(dimethylamino)benzyl titanium, (methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl allyl titanium,(phenylphosphido)(tetramethyl-η⁵ -cyclopentadienyl)methylene2-(dimethylaminomethyl)-phenyl titanium,(tert-butylamido)dibenzyl-(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl titanium, (benzylamido)dimethyl(η⁵-cyclopentadienyl)silane 2-(dimethylaminomethyl)phenyl titanium,(phenylphosphido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl titanium(III), (tert-butylamido)-dimethyl(η⁵-tetramethylcyclopentadienyl)silane allyl titanium,(phenylamido)-phenylmethyl(η⁵ -tetrahydroindenyl)silane2-(dimethylamino)benzyl titanium, (methylamido)cyclotetramethylene(η⁵-octahydrofluorenyl)silane 2-(dimethylamino)benzyl titanium,cyclopentadienyl-methyl 2-(dimethylamino)benzyl titanium,(tert-butylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl zirconium, (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl zirconium,(tert-butylamido)(tetramethyl-η⁵ -cyclopentadienyl)-1,2-ethanediyl allylzirconium, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl 2-(dimethylamino)benzylzirconium,(methylamido) (η⁵ -cyclopentadienyl)-1,2-ethanediyl2-(dimethylamino)benzyl zirconium, (methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl allyl zirconium,(phenylphosphido)(tetramethyl-η⁵ -cyclopentadienyl)methylene2-(dimethylaminomethyl)phenyl zirconium,(tert-butylamido)dibenzyl(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl zirconium, (benzylamido)dimethyl(η⁵-cyclopentadienyl)silane 2-(dimethylaminomethyl)phenyl zirconium,(phenylphosphido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl zirconium, (tert-butylamido)dimethyl(η⁵-tetramethylcyclopentadienyl)silane allyl zirconium,(phenylamido)phenylmethyl(η⁵ -tetrahydroindenyl)silane2-(dimethylamino)benzyl zirconium, and(methylamido)cyclotetramethylene(η⁵ -octahydrofluorenyl)silane2-(dimethylamino)benzyl zirconium.

Preferred cyclic complexes, A₃, are amidosilane- or amidoalkanediyl-compounds corresponding to the formula: ##STR5## wherein:

M, L", E, R', and R" are as previously defined;

Y' is nitrogen;

R'" is a group selected from silyl, hydrocarbyl and combinationsthereof, said group or combination having up to 30 carbon or siliconatoms; and

m is 1 or 2.

Preferably R'" is methyl, ethyl, propyl, butyl, pentyl, hexyl,(including where appropriate all isomers), cyclopentyl, cyclohexyl,norbornyl, benzyl, or phenyl.

In the most preferred embodiment --(ER"₂)_(m) Y'R'"-- an amidosilane oramidoalkane group of up to 30 nonhydrogen atoms, especially,(tert-butylamido)(dimethylsilyl), (methylamido)(dimethylsilyl), or(tert-butylamido)-1-ethane-2-yl.

Other complexes which are useful in the catalyst compositions of thisinvention will be apparent to those skilled in the art.

Highly preferably in complexes A₁, M is titanium and L is2-dimethylaminobenzyl. Highly preferably in complexes A₂, M is titaniumand L' is 2-dimethylaminobenzyl or allyl. Highly preferably in complexesA₃, M is titanium and L" is 2-dimethylaminobenzyl or allyl.

By the term "reducing agent" herein is meant a metal or compound which,under reducing conditions causes M to be reduced from the +4 oxidationstate to the +3 oxidation state. Examples of suitable metal reducingagents are alkali metals, alkaline earth metals, lead and zinc, alloysof alkali metals or alkaline earth metals such as sodium/mercury amalgamand sodium/potassium alloy. Examples of suitable reducing agentcompounds are sodium naphthalenide, potassium graphite, Grignardreagents, and the like. Most preferred reducing agents are the alkalimetals or alkaline earth metals, especially magnesium.

By the term "reducing conditions" is meant the use of diluents andtemperatures that allow the desired reduction to take place. Preferredtemperatures are from 0° C. to 200° C., more preferably from 5° C. to120° C. most preferably from 10° C. to 50° C. Preferred diluents arepolar solvents, more preferably C₁₋₆ aliphatic ethers, most preferablytetrahydrofuran, 1,2-dimethoxyethane or diethyl ether.

The term "activating cocatalyst" as used herein refers to a secondarycomponent that renders the metal complex catalytically effective orimproves the catalytic effectiveness of the metal-containing complex asan addition polymerization catalyst. Examples of the activatingcocatalysts for use herein include aluminum compounds containing anAl--O bond such as the alkylalumoxanes, especially methylalumoxane andisobutyl modified methylalumoxane; aluminum alkyls; aluminum halides;alkylaluminum halides; Lewis acids other than any of the foregoing list;and mixtures of the foregoing.

Preferred Lewis acids are those compounds corresponding to the formula:R""₃ B, wherein R"" independently each occurrence is selected fromhydrogen, silyl, hydrocarbyl, halohydrocarbyl, alkoxide, aryloxide,amide or combinations thereof, said R"" having up to 30 nonhydrogenatoms.

It is to be appreciated by those skilled in the art, that the aboveformula for the preferred Lewis acids represents an empirical formula,and that many Lewis acids exist as dimers or higher oligomers insolution or in the solid state. Other Lewis acids which are useful inthe catalyst compositions of this invention will be apparent to thoseskilled in the art.

Preferred activating cocatalysts include trimethylaluminum,triisobutylaluminum, methylalumoxane, ethylalumoxane,chlorodiethylaluminum, dichloroethylaluminum, triethylboron,trimethylboron, triphenylboron and halogenated, especially fluorinated,triphenyl boron compounds.

Most highly preferred activating cocatalysts include triethylaluminum,methylalumoxane, and fluoro-substituted triaryl borons such astris(4-fluorophenyl)boron, tris(2,4-difluorophenylboron),tris(3,5-bis(trifluoromethyl)phenyl)boron, tris(pentafluorophenyl)boron,pentafluorophenyldiphenylboron, and bis(pentafluorophenyl)phenylboron.Such fluoro-substituted triarylboranes may be readily synthesizedaccording to techniques such as those disclosed in Marks, et al. J. Am.Chem. Soc., 113, 3623-3625 (1991).

The catalyst can be utilized by forming the metal complex and whererequired combining the activating cocatalyst with the same in a diluent.The preparation may be conducted in the presence of one or more additionpolymerizable monomers, if desired. Preferably, the catalysts areprepared at a temperature within the range from -100° C. to 300° C.,preferably 0° C. to 250° C., most preferably 0° C. to 100° C. Suitablesolvents include straight and branched-chain hydrocarbons such asisobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinatedhydrocarbons such as perfluorinated C₄₋₁₀ alkanes and aromatic andalkyl-substituted aromatic compounds such as benzene, toluene andxylene. Suitable solvents also include liquid olefins which may act asmonomers or comonomers including ethylene, propylene, butadiene,cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene,4-vinylcyclohexene, allylbenzene and vinyltoluene (including all isomersalone or in admixture). Preferred solvents are aliphatic hydrocarbonsespecially C₅ -C₁₀ alkanes or cycloalkanes and mixtures thereof. Such amixture is available commercially under the trade designation Isopar™E,available from Exxon Chemicals.

"Addition polymerizable monomers" usefully polymerized according to thepresent invention include, for example, ethylenically unsaturatedmonomers, cyclic olefins, acetylenic compounds, conjugated ornonconjugated dienes and polyenes, etc. Examples include C₂₋₂₀ olefins,styrene, halo- or hydrocarbyl substituted styrenes, divinylbenzene,4-vinylcyclohexene, tetrafluoroethylene, vinylbenzocyclobutane,butadiene, isoprene, 1,4-hexadiene, cyclobutene, cyclopentene,cyclohexene, norbornene, ethylidene norbornene, and mixtures thereof.Preferred monomers include the C₂₋₁₀ α-olefins especially ethylene,propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene,and 1-octene.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0° to 250° C. andpressures from atmospheric to 1000 atmospheres (100 MPa). Suspension,solution, slurry, gas phase or other process condition may be employedif desired. The catalyst may be supported and such supported catalystmay be employed in the polymerizations of this invention. Preferredsupports include alumina and silica.

The equivalent ratio of metal complex to activating cocatalyst (whereemployed) is preferably in a range from 1:0.5 to 1:10⁴, more preferablyfrom 1:0.75 to 1:10³, most preferably 1:1 to 1:10. In mostpolymerization reactions the equivalent ratio of catalyst:polymerizablecompound employed is from 10⁻¹² :1 to 10⁻¹ :1, more preferably from 10⁻⁹:1 to 10⁻⁴ :1.

Surprisingly and contrary to teachings in the prior art, homogeneous,reduced, Group 4 metal catalysts have been discovered to be highlyactive addition polymerization catalysts.

Having described the invention the following examples are provided asfurther illustration thereof and are not to be construed as limiting.Unless stated to the contrary all parts and percentages are expressed ona weight basis.

EXAMPLES 1-58

i) Preparation Of Reduced MetalComplex--(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium, (CH₃)₄ C₅Si(CH₃)₂ N --C(CH₃)₃)Ti(o--CH₂ C₆ H₄ N(CH₃)₂) ##STR6##

In the drybox, 1.65 g (4.45 mmol) of TiCl₃ (THF)₃ and 2.29 g (4.46 mmol)of (MgCl)₂ ((CH₃)₄ C₅ Si(CH₃)₂ N--C(CH₃)₃)(THF)₂ were mixed together ina 100 mL flask. Tetrahydrofuran (THF) (50 mL) was added to give a purplesolution. After 15 minutes, 0.63 g (4.46 mmol) of o--LiCH₂ C₆ H₄ N(CH₃)₂was added. After 30 minutes, the volatile materials were removed underreduced pressure to yield a red-brown solid. Pentane (50 mL) was added,the solution was filtered, and the volume reduced to 40 mL. Thisconcentrated solution was cooled to -30° C. Red crystals were isolatedby filtration and dried under reduced pressure.

The electron paramagnetic resonance (EPR) spectrum of this materialexhibited a single line at room temperature (g=1.974) and 2 lines at77K. The X-ray crystal structure had final cell parameters correspondingto a triclinic unit cell. Cell parameters were: a=9.922(4), b=14.366(9),c=9.857(5) (angstroms); α=104.35(6), B=111.69(4), Y=99.61(6); V=1212(1)(angstroms³).

ii) Alternate preparation of (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium--reduction ofTi(IV) complex.

In an argon filled glovebox, 0.990 g (2.69 mmol) of(tert-butylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silanetitanium dichloride (prepared by use of an organic halide oxidantaccording to the teachings of U.S. Ser. No. 702,475, filed May 20, 1991,the teachings of which are incorporated herein by reference) and 0.389 g(2.76 mmol) of Li(o--CH₂ (C₆ H₄)N(CH₃)₂) were mixed together in a 100 mLflask. Pentane (75 mL) was added and the mixture stirred for 16 hours toprovide an orange colored product. The mixture was filtered through asintered glass frit. The solids were washed with pentane and thefiltrates combined. Pentane solvent was removed under reduced pressureleaving a solid residue which was washed with cold pentane. The pentanewash was decanted from the residue and the product dried under reducedpressure giving 0.96 g. of an orange solid. ¹ H NMR analysis confirmedthe product's identity as (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane titanium 2-(dimethylamino)benzyl chloride.Yield was 76 percent.

The solid product (0.490 g, 1.05 mmole) obtained above was added to 50ml of tetrahydrofuran. Magnesium powder (30 mg) was then added. Themixture was allowed to stir at 25° C. After 30 minutes the orange colorof the solution changed to brown. After 4 hours the solvent was removedunder reduced pressure. The solid residue was extracted with pentane(3×25 ml). The pentane extracts were filtered through a sintered glassfrit, combined, and the pentane removed under reduced pressure to give0.452 g (quantitative yield) of rose-purple microcrystalline solid,identified as (tertbutylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium by comparisonof its cyclic voltamagram with that of the material obtained inPreparation i.

iii) Preparation of Reduced MetalDerivative--(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane allyl titanium (III), ((CH₃)₄ C₅ Si(CH₃)₂NC(CH₃)₃)Ti(C₃ H₅).

In the drybox, 0.30 g of TiCl₃ (THF)₃ and 0.42 g of (MgCl)₂ ((CH₃)₄ C₅Si(CH₃)₂ N--C(CH₃)₃)(THF)₂ were mixed in a Schlenk tube. 20 mL of THFwas added to give a purple solution. The Schlenk tube was sealed andremoved to a Schlenk line, and the solution was cooled to -30° C. 0.81mL of 1.0M allylmagnesium bromide was added by syringe. After 20minutes, the solution was warmed to 0° C. and the volatile materialswere removed under reduced pressure to yield a dark solid. While keepingthe flask at 0° C. pentane (30 mL) was added, and the deep red solutionwas filtered, concentrated to ca. 5-7 mL, and cooled to -40° C. Redcrystals were isolated by filtration and dried in 22 percent yield. TheEPR spectrum of this material exhibited a single line at roomtemperature and 2 lines at 77K.

iv) Preparation of Reduced Metal Derivative--biscyclopentadienyl2-(dimethylamino)benzyl titanium (III), Cp₂ Ti(o--CH₂ C₆ H₄ N(CH₃)₂).

This metal complex was prepared according to the procedure of J. Am.Chem. Soc. 100, 8068-8073 (1978) by reaction of stoichiometric amountsof biscyclopentadienyltitanium (III) chloride and 2-dimethylaminobenzyllithium in diethylether.

v) Preparation of Reduced MetalDerivative--(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 1,2,3-trimethylallyl titanium (III).

In a glovebox under an inert atmosphere,(tertbutylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silanetitanium(IV) dichloride (0.500 g, 0.0014 mol) was dissolved in 3 ml of diethylether giving a yellow solution. To this solution was added3-methyl-1,3-pentadiene (0.31 ml, 0.0027 mol) and i-PrMgCl (1.18 ml,0.0045 mol). Gas evolution was noted and the color became red/purple.After 50 minutes the solvent was removed and the product dried.Extraction with pentane (5×10 ml) and drying under reduce pressure gavethe desired product as a red solid.

Polymerization

Several catalyst compositions were prepared by combining the metalcomplex and a cocatalyst in a stirred polymerization reactor. Thecocatalysts used were tris(perfluorophenyl)borane (I), methylalumoxane(1M in toluene, available from Schering (AG) (II), trimethyl aluminum(III), triisobutylaluminum (IV), isobutyl modified methylalumoxane (1Min toluene, MMAO, type 3A, available from Texas Alkyls Corp.) (V),triethylaluminum (VI), phenyl bisperfluorophenyl borane (VII), andtriphenyl borane (VIII). Accordingly, a 2 L stirred reactor was chargedwith the desired amounts of mixed alkane solvent (Isopar-E™ availablefrom Exxon Chemicals Inc.) and 1-octene comonomer. The reactor washeated to the polymerization temperature, hydrogen was added bydifferential pressure expansion from a ˜75 mL addition tank, and thereactor was saturated with ethylene to the desired pressure. Metalcomplex and cocatalyst (where used) were mixed in a drybox by syringingthe desired amount of 0.0050M metal complex solution (in Isopar-E™ ortoluene) into a solution of the cocatalyst (in Isopar-E™ or toluene).This solution was then transferred to a catalyst addition tank andinjected into the reactor. The same procedure was employed when nococatalyst was employed excepting only the complex was added to thereactor. The polymerization was allowed to proceed for the desired timeand the solution was removed from the reactor and quenched withisopropanol. A hindered phenol antioxidant (Irganox™ 1010, availablefrom Ciba Geigy Corp.) was added and the polymers (linear low densitypolyethylenes) were air-dried for 16 hours and then dried in a reducedpressure oven. Results are contained in Table I.

                                      TABLE I    __________________________________________________________________________        Com-            Amt.                Cocat-                     Amt.                         Solvent                              1-octene                                    Ethylene                                         H.sub.2                                             Temp Time                                                      Polymer                                                           Efficiency    Ex. plex            (μmol)                alyst                     (μmol)                         (g)  (g)   (MPa)                                         (Δkpa)                                             (°C.)                                                  (min)                                                      (g)  (g poly/g    __________________________________________________________________________                                                           Ti)     1  i   5.00                I    5.0 715  143   3.1  69  130  10  112.6                                                           470,146     2  i   5.00                I    5.0 715  143   "    69  130  10  8 3.2                                                           347,390     3  i   2.50                I    2.5 715  143   "    34  120  18  62.3 520,251     4  i   10.00                II   2940                         715  143   "    340 130  15  54.7 114,196     5  i   10.00                II   184 715  143   "    340 130  "   22.5 46,973     6  i   10.00                II   2940                         715  143   "    340 130  "   58.5 122,129     7  i   10.00                IV   1000                         715  143   "    340 1 30 "   23.7 49,478     8  i   10.00                II   1470                         787  72    "    34  160  "   17.8 37,161     9  i   10.00                II   2940                         787  72    "    0   175  "   13.6 28,392    10  i   10.00                II   7350                         715  143   "    340 130  "   53.7 112,109    11  iii 10.00                II   588 715  143   "    340 1 30 "   37.8 78,914    12  iii 10.00                II   441 715  143   "    340 1 30 "   23.1 48,225    13  i   0.50                I    1.5 740  118   3.4  170 100  "   62.2 2,597,077    14  i   1.50                I    3.0 788  70    "    90  160  "   20.0 285,317    15  i   1.00                I    3.0 740  118   "    340 14 0 "   30.7 640,919    16  i   1.00                I    3.0 740  118   "    0   14 0 "   18.7 390,397    17  i   0.75                I    1.5 691  167   "    90  1 20 "   45.5 1,266,527    18  i   0.75                I    1.5 788  70    "    260 120  "   44.8 1,247,042    19  i   0.75                I    3.0 691  167   "    90  120  "   43.2 1,202,505    20  i   1.00                I    3.0 740  118   "    170 140  "   17.2 359,081    21  i   1.50                I    6.0 788  70    "    260 1 60 "   12.4 172,582    22  i   0.75                I    1.5 788  70    "    90  120  "   41.6 1,157,968    23  i   1.00                I    3.0 740  118   "    170 14 0 "   10.1 210,856    24  i   0.75                I    3.0 788  70    "    90  1 20 "   45.2 1,258,177    25  i   1.00                I    3.0 740  118   "    170 140  "   16.3 340,292    26  i   1.00                I    3.0 740  118   3.4  170 140  15  12.6 263,048    27  i   10.00                I    30.0                         740  118   "    "   180  "   12.5 26,096    28  i   1.00                I    3.0 837  21    "    "   140  "   43.0 897,704    29  i   1.00                I    3.0 740  118   "    "   140  "   27.9 582,463    30  i   0.75                I    3.0 691  167   "    260 120  "   39.4 1,096,729    31  i   1.00                I    3.0 740  118   "    170 140  "   20.2 421,712    32  i   1.50                I    6.0 691  167   "    91  160  "   5.1  70,981    33  i   1.50                I    3.0 691  167   "    91  160  "   5.8  80,724    34  i   1.00                I    3.0 644  215   "    170 140  "   13.8 288,100    35  i   1.50                I    3.0 691  167   "    260 160  "   8.4  116,910    36  i   1.00                I    5.0 740  118   "    170 140  "   17.0 354,906    37  i   1.50                I    6.0 691  167   "    260 160  "   6.9  96,033    38  i   0.75                I    1.5 691  167   "    260 120  "   50.9 1,416,641    39  i   1.50                I    3.0 788  70    "    260 160  "   7.3  101,601    40  i   0.75                I    3.0 788  70    "    260 120  "   29.7 826,722    41  i   1.00                I    1.0 740  118   "    170 140  "   7.8  162,839    42  i   1.50                I    6.0 788  70    "    90  160  "   2.9  40,362    43  i   1.00                I    3.0 740  118   "    170 140  "   13.3 277,662    44  i   2.50                III  2.5 740  118   "    "   120  "   1.6  13,361    45  i   2.50                III  5.0 740  118   "    "   120  "   .7   5,846    46  i   2.50                III  7.5 740  118   "    "   120  "   0.7  5,846    47  i   2.50                IV   7.5 740  118   "    "   120  "   0.5  4,175    48  i   2.50                V    37.5                         740  118   "    "   120  "   3.3  20,577    49  i   2.50                VI   3.7 740  118   "    "   120  "   8.2  68,476    50  i   2.50                VI   7.5 740  118   "    "   120  "   8.9  74,322    51  i   2.50                VI   25.0                         740  118   3.4  170 120  15  9.1  75,992    52  i   2.50                VI   75.0                         740  118   "    "   "    "   5.7  47,599    53  iv  2.50                I    7.5 740  118   "    "   "    "   36.3 303,132    54  ii  2.00                I    30.0                         740  118   "    "   140  "   112.4                                                           1,174,000    55  ii  "   VII  3.0 "    "     "    "   140  "   122.4                                                           1,277,000    56  ii  "   VIII 3.0 "    "     "    "   140  "   119.5                                                           1,247,000    57  ii  "   --   0.0 "    "     "    "   "    "   72.3 755,000    58  v   0.75                1    0.75                         708  150   "    "   120  "   68.8 1,915,000    __________________________________________________________________________

EXAMPLE 58

Preparation of (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium chloride

In an argon filled glove box, 0.55 g (1.29 mmol) of(phenylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane titaniumdichloride (prepared according to example 89 of U.S. Ser. No. 545,403filed Jul. 3, 1990) and 0.18 g (1.3 mmol) of 2-(dimethylamino)benzyllithium were slurried in ˜75 mL of pentane. The mixture turned fromyellow to red after ˜16 hours. The mixture was filtered and the solidswere extracted with diethyl ether. The pentane and ether fractions weredevolatilized under reduced pressure. ¹ H NMR analysis confirmed theproduct's identity from both fractions as(phenylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane titanium2-(dimethylamino)benzyl chloride. Total yield was 0.33 g, 53 percent.

Preparation of (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane-2-(dimethylamino)benzyl titanium

In an argon filled glove box 16 mg of magnesium powder was added to 0.33g (0.68 mmol) of (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium chloride in˜40 mL of tetrahydrofuran (THF). After stirring for 6 hours the THF wasremoved under reduced pressure. The solid residue was extracted withpentane. The pentane extracts were filtered and combined and the pentanesolvent removed under reduced pressure to give 0.29 g (94 percent yield)of (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane-2-(dimethylamino)benzyl titanium, characterizedby cyclic voltametry.

We claim:
 1. An addition polymerization catalyst comprising incombination:a metal complex corresponding to the formula

    Cp'ML'.sub.2,

wherein:Cp' is a cyclopentadienyl group n-bound to M, or a hydrocarbyl,silyl, halo, halohydrocarbyl, or hydrocarbylmetalloid substitutedderivative thereof, said Cp' containing up to 50 nonhydrogen atoms; M istitanium in the ⁺ 3 oxidation state; L' independently each occurrence ishydride, halo, or a monovalent anionic ligand selected from the groupconsisting of hydrocarbyl, silyl, amido, phosphido, alkoxy, aryloxy, andsulfido groups; mixtures thereof; and amine, phosphine, ether, andthioether derivatives of the foregoing, said ligand having up to 50nonhydrogen atoms, with the proviso that in at least one occurrence L'is a stabilizing ligand comprising an amine, phosphine, ether orthioether functionality able to form a coordinate-covalent bond orchelating bond with M, or comprising an ethylenic unsaturation able toform an η3 bond with M; and an activating cocatalyst.
 2. A catalyst asclaimed in claim 1, wherein M is titanium, and L is2-(dimethylamino)benzyl or allyl.
 3. A catalyst according to claim 1wherein the ratio of metal complex to activating cocatalyst is from1:0.01 to 1:10⁶.
 4. A catalyst as claimed in claim 1 wherein theactivating cocatalyst is selected from the group consisting ofalkylalumoxanes, aluminum alkyls, aluminum halides, alkylaluminumhalides, Lewis acids other than any of the foregoing, and mixturesthereof.
 5. A catalyst as claimed in claim 4, wherein the activatingcocatalyst is tris(4-fluorophenyl)boron, tris(2,4-difluorophenylboron),tris(3,5-bis(trifluoromethyl)phenyl)boron, tris(pentafluorophenyl)boron,pentafluorophenyl diphenylboron, triphenyl boron orbis(pentafluorophenyl)phenylboron.
 6. A catalyst as claimed in claim 2,wherein the activating cocatalyst is tris(pentafluorophenyl)boron.
 7. Anaddition polymerization catalyst comprising:1) a complex correspondingto the formula: ##STR7## wherein: M is titanium in the +3 oxidationstate;Cp" is a cyclopentadienyl group, or a hydrocarbyl, silyl, halo,halohydrocarbyl, or hydrocarbylmetalloid substituted derivative thereof,said Cp" containing up to 50 nonhydrogen atoms; Z is a divalent moietycomprising oxygen, nitrogen, phosphorous, boron, or a member of Group 14of the Periodic Table of the Elements said moiety having up to 30nonhydrogen atoms; Y is a linking group comprising nitrogen, phosphorus,oxygen or sulfur covalently bonded to M and Z through said nitrogen,phosphorus, oxygen or sulfur atom, the ligand moiety consisting of--Cp"--Z--Y-- being dianionic and having the ionic charges residingformally on Cp" and Y; and L" is a monovalent anionic stabilizing ligandselected from the group consisting of: a) alkyl, cycloalkyl, aryl,silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups and mixturesthereof, and being further substituted with an amine, phosphine, ether,or thioether containing substituent able to form a coordinate-covalentbond or chelating bond with M, said ligand having up to 50 nonhydrogenatoms; and b) C₃₋₁₅ hydrocarbyl groups comprising an ethylenicunsaturation able to form an η³ bond with M; and 2) an activatingcocatalyst.
 8. An addition polymerization catalyst according to claim 7,wherein the activating cocatalyst is selected from the group consistingof alkylalumoxanes; aluminum alkyls; aluminum halides; alkylaluminumhalides, Lewis acids other than any of the foregoing; and mixturesthereof.
 9. An addition polymerization catalyst as claimed in claim 8,wherein the activating cocatalyst is tris(4-fluorophenyl)boron,tris(2,4-difluorophenylboron),tris(3,5-bis(trifluoromethyl)phenyl)boron, tris(pentafluorophenyl)boron,pentafluorophenyl diphenylboron, triphenyl boron orbis(pentafluorophenyl)phenylboron.
 10. An addition polymerizationcatalyst comprising a complex selected from the group consisting of(tert-butylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane2-(dimethylamino)benzyl titanium (III),(tert-butylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silane allyltitanium (III), and (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane 1,2,3-trimethylallyl titanium (III), andtris(pentafluorophenyl)boron activating cocatalyst.